Olive-tree polyphenols and urban mining. A greener alternative for the recovery of valuable metals from scrap printed circuit boards.

Recycling printed circuit boards (PCBs) is becoming a source of precious metals and an alternative to conventional mining. This phenomenon is now known as "urban mining." In this work, a polyphenols-rich plant extract has been obtained from olive-tree leaves, and its ability to contribute to reducing four metals, namely, Ag, Cu, Cr, and Sn, that are present in scrap PCBs has been studied. Three reductants (NaBH4, Fe°, and the olive-tree leaves extract) have been used to recover these valuable metals. An attempt has been made to minimize the concentration of the first two, replacing them with a natural, cheaper, and less toxic reductant. To achieve this goal, a computer-assisted factorial, composed, centered, orthogonal, and rotatable statistical design of experiments (FCCORD) has been used to build the experimental matrix to be carried out in the laboratory and, next, for the statistical treatment of the results. The results show that it is possible to achieve only a partial recovery of the four metals (silver, copper, chromium, and tin) from PCBs leachates by using sodium borohydride, iron, and the extract separately. In other words, none of these three reductants alone can completely remove any of the four metals in the leachate. Nevertheless, using the statistical design of experiments, the total recovery of the four metals has been achieved by combining the three reductants in the appropriate concentrations. Hence, polyphenols-rich plant extracts in general and olive-tree leaves extract in particular can be regarded as promising coadjuvants in the rising field of urban mining.

Electrochemical and sonochemical advanced oxidation processes applied to tartrazine removal. Influence of operational conditions and aqueous matrix.

Tartrazine degradation was investigated by electrochemical and sonochemical oxidation processes. Anodic oxidation was carried out using boron-doped diamond (BDD) electrodes. The influence of current density and dye initial concentration on the removal of tartrazine from water was analyzed. The experimental results indicate that total removal of tartrazine was obtained, and Chemical Oxygen Demand (COD) and Total Organic Carbon (TOC) removals of up to 94.4% and 72.8% were achieved, respectively. To optimize the process, the pollutant removal percentage, the kinetic rate constant, and the TOC removal efficiency were chosen as target variables. Moreover, sonochemical oxidation experiments at a high-frequency range of cavitation (up to 1 MHz) were performed to establish the influence of three different operating variables, namely ultrasound frequency (0.5-1.1 MHz), ultrasound power (2.0-26.6 W ⋅L-1), and pulse-stop ratio (5:1-1:1). The process was also analyzed in terms of kinetics and energy costs. The kinetics resulted to be three times faster for the electrochemical process. However, the calculated energy costs were very similar, at least at long treatment times. Finally, the influence of three aqueous matrices was investigated. According to the experimental results, the natural occurrence of chloride and/or nitrate ions in water strongly conditions the rate of the process, although at least 90% of tartrazine removal was achieved within the first 50 min of treatment.

Preparation of high-quality activated carbon from polyethyleneterephthalate (PET) bottle waste. Its use in the removal of pollutants in aqueous solution.

A waste-treats-waste approach has been used for the removal of two common pollutants, namely p-nitrophenol and/or Fe(III) from aqueous solution. Polyethyleneterephthalate (PET) from bottle waste has been used as the precursor for the preparation of activated carbons (ACs) by physical activation with steam and chemical activation with potassium hydroxide under controlled heating conditions and atmospheres. The resulting ACs were characterized in terms of chemical composition, porous texture and surface chemistry, and morphology. Selected ACs were tested as adsorbents for the removal of the aforementioned pollutants in aqueous solution. For comparison purposes, a commercial AC was also used. In general, the yield of the process of preparation of ACs is lower than 10% with steam and between 24.62 and 32.07% with potassium hydroxide. ACs possess a very high carbon content and a very low ash content. The BET surface areas reach 1235 m(2) g(-1) with steam and 1002 m(2) g(-1) with potassium hydroxide at most. Also, the degrees of development of micro- and mesoporosity are markedly larger with steam. Conversely, the development of macroporosity is much larger with potassium hydroxide. The PET-derived ACs exhibit a better adsorption behavior towards p-nitrophenol than the commercial AC, both in terms of adsorption rate and adsorption capacity. On the contrary, the commercial AC acts as a better adsorbent of Fe(III) ions. As compared to separately, the simultaneous presence of both solutes in the adsorptive solution scarcely affects the adsorption process except for equilibrium for Fe(III).

Comparative valorisation of agricultural and industrial biowastes by combustion and pyrolysis.

Combustion and pyrolysis processes were assessed and compared for two types of lignocellulosic biowastes: agricultural (Eucalyptus bark, grape seeds, peach stones, walnut shells, olive waste and peanut shells) and industrial (primary and biological paper mill sludge) biowastes. They were characterized by elemental, proximate and thermal analyses; the pyrolysis behaviour was studied by thermogravimetric analysis and the gases produced were identified using mass spectrometry. Agricultural biowastes showed the highest calorific values, close to the fossil fuel values (20-30MJkg(-1)) and, in general, emission of gases containing the carbon element (CH4, C2H2, CO and CO2) was higher than that of the tested industrial biowastes, making the agricultural biowastes highly competitive for combustion applications such as gas fuel. Further, the solid product which resulted from the pyrolysis of industrial biowastes is a material with large specific surface area, which is a good characteristic for possible applications as adsorbent in water remediation.

Parabens abatement from surface waters by electrochemical advanced oxidation with boron doped diamond anodes.

The removal efficiency of four commonly-used parabens by electrochemical advanced oxidation with boron-doped diamond anodes in two different aqueous matrices, namely ultrapure water and surface water from the Guadiana River, has been analyzed. Response surface methodology and a factorial, composite, central, orthogonal, and rotatable (FCCOR) statistical design of experiments have been used to optimize the process. The experimental results clearly show that the initial concentration of pollutants is the factor that influences the removal efficiency in a more remarkable manner in both aqueous matrices. As a rule, as the initial concentration of parabens increases, the removal efficiency decreases. The current density also affects the removal efficiency in a statistically significant manner in both aqueous matrices. In the water river aqueous matrix, a noticeable synergistic effect on the removal efficiency has been observed, probably due to the presence of chloride ions that increase the conductivity of the solution and contribute to the generation of strong secondary oxidant species such as chlorine or HClO/ClO -. The use of a statistical design of experiments made it possible to determine the optimal conditions necessary to achieve total removal of the four parabens in ultrapure and river water aqueous matrices.

Advanced photochemical oxidation of emergent micropollutants: carbamazepine.

The combination of UV radiation with hydrogen peroxide has been widely used for the photodegradation of pollutants in aqueous solutions. Statistical design of experiments is a powerful tool to optimize this kind of process. Initial hydrogen peroxide concentration, pH and temperature were considered as the variables for the process optimization. The interactions existing between these three variables were analyzed. Initial concentration of hydrogen peroxide proved to be the most important variable conditioning the removal efficiency, followed by temperature, and pH shows a non-significant positive influence along the whole operation interval. The ANOVA test reported significance for five of the nine involved variables. The Response Surface Methodology technique was used to optimize carbamazepine degradation. Under optimal conditions (hydrogen peroxide concentration = 0.38·10(-3) mol L(-1), pH = 1 and temperature = 35.6°C) total carbamazepine degradation was achieved.

Feasibility of electrochemical degradation of pharmaceutical pollutants in different aqueous matrices: optimization through design of experiments.

Electrochemical degradation of different effluents polluted with carbamazepine, a well-known refractory pharmaceutical contaminant, was addressed in this article. Ultrapure water (Milli-Q(TM) technology), surface water from a lake and urban wastewater were the matrices used to evaluate the feasibility of performing the electro-oxidation of carbamazepine. Specific designs of experiments were planned for each of the aqueous media. The initial carbamazepine concentration and the electric current density were considered as the operational variables. Although the optimal values of both variables follow the same trend in the three cases, significant differences are observed regarding the comparative influence of each variable on the degradation of carbamazepine.

Influence of the operation conditions on CO2 capture by CaO-derived sorbents prepared from synthetic CaCO3.

In this work, a statistical experimental design is performed in order to prepare CaCO3 materials for use as CaO-based CO2 sorbent precursors. The influence of different operational parameters such as synthesis temperature (ST), stirring rate (SR) and surfactant percent (SP) on CO2 capture is studied by applying Response Surface Methodology (RSM). The samples were characterized using different analytical techniques including X-ray diffraction, N2 adsorption isotherm analysis and Scanning Electron Microscopy-X-ray Energy Dispersive Spectroscopy (SEM-EDX). CO2 capture capacity was determined by means of a thermogravimetric analyzer which recorded the mass uptake of the samples when these were exposed to a gas stream containing diluted (15%) CO2. The statistical approach used in this work provides a rapid way of predicting and optimizing the main preparation variables of CaO-derived sorbents for CO2 sorption. The results obtained clearly indicate that four parameters statistically influence CO2 uptake: SR, the square of SR, its interaction with SP and the square of SP.

On the use of a natural peat for the removal of Cr(VI) from aqueous solutions.

A natural peat has been used as an adsorbent for the removal of hexavalent chromium from aqueous solution. The peat was firstly characterized in terms of particle size and chemical composition (ash content, pH of the point of zero charge, FT-IR and thermal analysis). Next, the kinetic and equilibrium aspects of the adsorption of Cr(VI) by this adsorbent were studied. The kinetic data were satisfactorily fitted to a kinetic law of partial order in C equal to one. The specific adsorption rates are around 10(-4)s(-1), increasing as temperature does. A noticeable influence of diffusion on the global adsorption process has been demonstrated. Finally, the equilibrium isotherms were satisfactorily fitted to a previously proposed model. The adsorption capacity of Cr(VI) was similar to some other previously reported and the affinity of Cr(VI) towards the active sites of the adsorbent increases as temperature rises.

On the use of carbon blacks as potential low-cost adsorbents for the removal of non-steroidal anti-inflammatory drugs from river water.

The adsorption of two non-steroidal anti-inflammatory drugs (NSAIDs), namely naproxen and ketoprofen, has been studied. Low-cost carbonaceous materials such as carbon blacks have been used as the adsorbents. The influence of temperature (20-60 degrees C), pH (3-11), ionic strength (0.01-0.1M), textural properties of the adsorbents (S(BET) and pore volumes) and aqueous matrix on the adsorption process has been analyzed. The adsorption isotherms have been determined both in milli-Q aqueous solution and water from the Guadiana river. Ionic strength and pH exert a noticeable influence on the process. In general, the removal is favored at low values of temperature and pH. On the contrary, an increase of the ionic strength seems to favor the adsorption process. The use of more porous adsorbents results in a more effective removal of the pollutants. Finally, the use of natural river water results in a noticeable increase of the removal capacity of naproxen and, particularly, ketoprofen. The experimental results proved that, under the optimal operation conditions, up to 517mg/g of naproxen and 400mg/g of ketoprofen may be adsorbed, which demonstrates the promising potential of these adsorbents for the removal of the pharmaceuticals under study.

Removal of chlorophenols in aqueous solution by carbon black low-cost adsorbents. Equilibrium study and influence of operation conditions.

The adsorption process of chlorophenols (CPs) by low-cost adsorbents such as carbon blacks has been studied. The influence of different parameters such as temperature, pH, ionic strength and textural properties of the adsorbents on the adsorption process of pentachlorophenol has been analyzed. The adsorption process is exothermal and parameters such as pH and ionic strength exert a noticeable influence on the adsorption capacity of the solute. These parameters influence the adsorption capacity in an opposite manner. Thus an increase in pH seems to unfavor the adsorption process, whereas the adsorption capacity increases with increasing ionic strength. In order to analyze the influence of the number of chlorine atoms in the molecule of solute the adsorption process of different chlorophenols (i.e., 4-chlorophenol, 3,5-dichlorophenol, 2,4,6-trichlorophenol and 2,3,4,6-tetrachlorophenol) was analyzed. As the number of chlorine atoms (and thus the volume of the molecule) increases, the penetration of the solute through the porous texture of the adsorbent is difficult and, consequently, the adsorption capacity decreases.

Adsorption of Zn(II) in aqueous solution by activated carbons prepared from evergreen oak (Quercus rotundifolia L.).

In the present work activated carbons have been prepared from evergreen oak wood. Different samples have been prepared varying the concentration of the activating agent (H(3)PO(4)) and the treatment temperature. The yield of the process decreases with increasing phosphoric acid concentrations. Furthermore, high concentrations of activating agent lead to mainly mesoporous activated carbons to the detriment of the microporous texture. Treatment temperatures up to 450 degrees C lead to a progressive increase of the micro- and mesopore volumes. Values of specific surface area (S(BET)) as high as 1723 m(2) g(-1)have been obtained using appropriate phosphoric acid concentrations and treatment temperatures. The samples prepared have been successfully used in the removal of Zn(II) from aqueous solutions. From the adsorption kinetic data it may be stated that the equilibrium time is, in all cases, below 170 h. The adsorption process as a rule becomes faster as the mesopore volume and specific surface area of the samples increase. The adsorption isotherms in liquid phase point out that the adsorption capacity (n(0)(s)) and the affinity towards the solute (K(ci)) are higher for the sample showing the most developed mesoporous texture and surface area as well.